CN1052923C - A kind of preparation method of fluorite flotation agent - Google Patents
A kind of preparation method of fluorite flotation agent Download PDFInfo
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 239000010436 fluorite Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000008396 flotation agent Substances 0.000 title abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 35
- 229930195729 fatty acid Natural products 0.000 claims abstract description 35
- 239000000194 fatty acid Substances 0.000 claims abstract description 35
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 35
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000005642 Oleic acid Substances 0.000 claims description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 21
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KOPMZTKUZCNGFY-UHFFFAOYSA-N 1,1,1-triethoxybutane Chemical compound CCCC(OCC)(OCC)OCC KOPMZTKUZCNGFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 claims 1
- 230000001180 sulfating effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 238000005670 sulfation reaction Methods 0.000 abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 9
- 239000011707 mineral Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 238000005188 flotation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 triethoxybutane Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本发明涉及一种萤石选厂浮选剂的制备方法，具体地说就是采用目前萤石浮选厂普遍采用的萤石浮选捕收剂——油酸生产过程中的中间产品粗脂肪酸或混合脂肪酸为基本原料制备萤石浮选剂的方法。The invention relates to a preparation method of a flotation agent in a fluorite separation plant, specifically, the fluorite flotation collector commonly used in fluorite flotation plants—the intermediate product crude fatty acid or oleic acid in the production process of oleic acid A method for preparing fluorite flotation agent by mixing fatty acids as basic raw materials.
目前，国内外萤石选厂普遍采用的浮选捕收剂为油酸。油酸可以用食用油为原料加工生产，但由于食用油价格高且资源有限，因而近年一些厂家改用油脚或酸化油为原料加工生产油酸。这里的油脚是指油厂加工食用动植物油所产生的副产品，即分去成品油后的乳化层及沉渣；酸化油是指油脚经初步酸化水解加工所得到的脂肪酸及未水解油的混合物，酸价为110～130毫克(毫克kOH/克样)。At present, the flotation collector commonly used in domestic and foreign fluorite concentrators is oleic acid. Oleic acid can be processed and produced from edible oil, but due to the high price of edible oil and limited resources, in recent years, some manufacturers have switched to oil foot or acidified oil as raw material to process and produce oleic acid. The oil foot here refers to the by-products produced by the processing of edible animal and vegetable oil in the oil factory, that is, the emulsified layer and sediment after the refined oil is separated; the acidified oil refers to the mixture of fatty acids and unhydrolyzed oil obtained from the initial acidification and hydrolysis of the oil foot , the acid value is 110-130 mg (mg kOH/g sample).
制备油酸的通用工艺流程为：原料油脚或酸化油在酸性或碱性条件下水解，生成粗脂肪酸；粗脂肪酸分去水层后，经干燥脱水、蒸馏，产出约占粗脂肪酸量85％的混合脂肪酸，同时产生副产品釜底蒸留物；混合脂肪酸经冷冻压榨，产出最终产品油酸，其产量约占混合脂肪酸量65％～75％，同时产出副产固体酸。The general process for preparing oleic acid is as follows: raw oil bottoms or acidified oil are hydrolyzed under acidic or alkaline conditions to generate crude fatty acid; after the crude fatty acid is removed from the water layer, it is dried, dehydrated, and distilled, and the output accounts for about 85% of the crude fatty acid. % of mixed fatty acids, while producing by-product still bottoms; mixed fatty acids are frozen and pressed to produce the final product oleic acid, which accounts for about 65% to 75% of the amount of mixed fatty acids, and simultaneously produces solid acids as a by-product.
从以上油酸生产的工艺流程看出，油酸生产的周期长，蒸馏和冷冻压榨能耗大，而且产出两种价值很低或较低的蒸馏残渣和固体酸，最终产品油酸占最初中间产品粗脂肪酸的比例只有约50％～65％，这就使得油酸的价格变得昂贵，从而增加了使用油酸的萤石浮选厂的生产成本。不仅如此，有些厂家因冷冻压榨不完善，往往产出含固体酸较多的油酸，采用这种油酸作萤石浮选捕收剂，在低温条件下，选别效果显著变差，捕收能力大幅度下降。From the above process of oleic acid production, it can be seen that the production cycle of oleic acid is long, the energy consumption of distillation and freezing pressing is large, and two kinds of distillation residue and solid acid with very low or low value are produced. The final product oleic acid accounts for the initial The proportion of crude fatty acid in the intermediate product is only about 50% to 65%, which makes the price of oleic acid expensive, thereby increasing the production cost of the fluorite flotation plant using oleic acid. Not only that, some manufacturers often produce oleic acid containing more solid acids due to imperfect freezing and pressing. If this oleic acid is used as a fluorite flotation collector, the separation effect will be significantly worse under low temperature conditions, and the collection effect will be significantly worse. The ability to collect has dropped significantly.
本发明的目的就是针对油酸在生产上以及在萤石浮选应用中存在的上述问题，而提出的一种生产成本低廉、药剂捕收能力强，适于低温浮选的萤石浮选剂的制备方法。The purpose of the present invention is to solve the above-mentioned problems in the production of oleic acid and in the application of fluorite flotation, and propose a fluorite flotation agent with low production cost, strong reagent collection ability, and suitable for low temperature flotation. method of preparation.
本发明萤石浮选剂的制备方法按以下工艺、步骤进行；以油酸生产的中间产品粗脂肪酸或混合脂肪酸为原料，其酸价应大于(165毫克KOH/克样)，不饱和酸含量≥80％，向其加入重量为脂肪酸重量3％～15％的浓硫酸，控制反应温度在20℃～40℃，反应时间40～90分钟；硫酸化反应完毕后，经洗涤、静置、分去水层，再加入重量为脂肪酸重量0.4％～3％的选矿起泡剂，混合均匀即成为成品。The preparation method of the fluorite flotation agent of the present invention is carried out according to the following processes and steps; the intermediate product crude fatty acid or mixed fatty acid produced with oleic acid is used as raw material, and its acid value should be greater than (165 mg KOH/gram sample), and the unsaturated acid content ≥80%, add the concentrated sulfuric acid that weight is 3%～15% of fatty acid weight to it, control reaction temperature at 20 ℃～40 ℃, reaction time 40～90 minutes; Remove the water layer, then add a beneficiation foaming agent with a weight of 0.4% to 3% of the fatty acid weight, and mix evenly to become a finished product.
本发明提供的萤石浮选剂的制备方法，当所加浓硫酸量为脂肪酸重量的5％～8％为最佳。加入量过大，成品起泡能力太强，选择性下降；加入量太小，则硫酸化反应不充分。加入选矿起泡剂优先选用脂肪酸重量的0.5～1％。加入量过大，则起泡性太强，选择性变差；加入量过小，则降低了药剂的捕收性能。For the preparation method of the fluorite flotation agent provided by the invention, it is optimal when the amount of concentrated sulfuric acid added is 5% to 8% of the fatty acid weight. If the amount added is too large, the foaming ability of the finished product will be too strong and the selectivity will decrease; if the amount added is too small, the sulfation reaction will be insufficient. The addition of mineral dressing foaming agent is preferably 0.5-1% of the fatty acid weight. If the amount added is too large, the foaming property will be too strong and the selectivity will be poor; if the amount added is too small, the collection performance of the agent will be reduced.
上述加入的选矿起泡剂可以是醇类如萜烯醇、聚醇醚类如聚丙烯二醇醚、氧烷类如三乙氧基丁烷中的一种，或者是与上述几类选矿起泡剂具有相似性质的其他起泡剂，皆为本技术领域普通技术人员熟知。优先选用目前市场上广泛销售的选矿起泡剂2号油(醇类，主要成份及有效成份为萜烯醇)。The mineral dressing foaming agent added above can be one of alcohols such as terpene alcohol, polyalcohol ethers such as polypropylene glycol ether, oxanes such as triethoxybutane, or be combined with the above types of mineral processing Foaming Agents Other foaming agents having similar properties are well known to those of ordinary skill in the art. Preference is given to choosing No. 2 oil (alcohols, main and effective ingredients are terpene alcohols) of mineral dressing foaming agent widely sold on the market.
与油酸生产方法相比，采用本发明提供的方法制备萤石浮选剂，具有以下优点：Compared with the oleic acid production method, adopting the method provided by the invention to prepare fluorite flotation agent has the following advantages:
(1)不必排出价值低廉的副产，最大限度地利用了原料，降低了生产成本。(1) There is no need to discharge low-value by-products, the raw materials are utilized to the maximum extent, and the production cost is reduced.
(2)本发明生产的萤石浮选剂，其加工工艺与油酸制备工艺相比较，以40～90分钟的硫酸化反应，代替了制油酸的干燥脱水、蒸馏、冷冻压榨的长周期，大幅度地降低了能耗，因而降低了成本。(2) The fluorite flotation agent produced by the present invention, its processing technology is compared with the oleic acid preparation process, with the sulfation reaction of 40～90 minutes, has replaced the long cycle of dry dehydration, distillation, freezing press of oleic acid , greatly reducing energy consumption, thereby reducing costs.
(3)采用硫酸化处理，使原料中的部分不饱和脂肪酸发生硫酸化反应。硫酸化产物引进硫酸基团，可增加药剂对矿石的吸附，从而增加了药剂的捕收性能。硫酸化产物水溶性较好，它和熔点低的起泡剂一起加入到脂肪酸分子排列中，增加了药剂在矿浆中的乳化分散性，增加了在矿物表面的覆盖率，也就较大幅度地增加了药剂的捕收能力。(3) Sulfation treatment is adopted to make the partially unsaturated fatty acid in the raw material undergo sulfation reaction. Sulfation products introduce sulfuric acid groups, which can increase the adsorption of chemicals to ores, thereby increasing the collection performance of chemicals. The sulfated product has better water solubility, and it is added to the arrangement of fatty acid molecules together with a foaming agent with a low melting point, which increases the emulsification and dispersion of the agent in the pulp, increases the coverage on the mineral surface, and greatly improves the Increased the ability to collect potions.
(4)采用本方法制备的萤石浮选剂，因其乳化和溶解性能得到提高，水溶性、分散性较好，从而适于在常温或低温下浮选萤石。(4) The fluorite flotation agent prepared by this method is suitable for flotation of fluorite at normal temperature or low temperature because of its improved emulsification and solubility, good water solubility and dispersibility.
下面结合实施例，对本发明提供的方法作进一步详细的描述。The method provided by the present invention will be further described in detail below in conjunction with the examples.
实施例1Example 1
以油酸生产中的中间产品粗脂肪酸或混合脂肪酸为原料，用量为100克，其酸价大于165(毫克KOH/克样)，不饱和酸含量为80.0％，在不断搅拌下，加入3克的浓硫酸，采用冷却水冷却控制反应温度在35℃～40℃范围，加完浓硫酸后继续搅拌，总计40分钟，再加入20克的自来水，搅拌洗涤1分钟，静置1～2小时，待良好分层后分去水层，加入3克的选矿起泡剂2号油，混和均匀即成为产品。Use the intermediate product crude fatty acid or mixed fatty acid in the production of oleic acid as the raw material, the dosage is 100 grams, the acid value is greater than 165 (mg KOH/gram sample), and the unsaturated acid content is 80.0%, under constant stirring, add 3 grams Concentrated sulfuric acid, use cooling water to cool and control the reaction temperature in the range of 35°C to 40°C, continue stirring after adding the concentrated sulfuric acid, for a total of 40 minutes, then add 20 grams of tap water, stir and wash for 1 minute, and let stand for 1 to 2 hours. After good stratification, remove the water layer, add 3 grams of mineral dressing foaming agent No. 2 oil, and mix evenly to become the product.
实施例2Example 2
工艺条件为：原料脂肪酸的用量为100克，酸价大于175(毫克KOH/克样)，不饱和脂肪酸含量为85％，硫酸化反应温度在30℃～35℃范围，硫酸化反应时间为60分钟；浓硫酸加入量为7克；选矿起泡剂2号油加入量为1克。工艺步骤同实施例1。The process conditions are: the amount of raw fatty acid is 100 grams, the acid value is greater than 175 (mg KOH/gram sample), the unsaturated fatty acid content is 85%, the sulfation reaction temperature is in the range of 30°C to 35°C, and the sulfation reaction time is 60°C. minutes; the addition of concentrated sulfuric acid is 7 grams; the addition of No. 2 oil of mineral dressing foaming agent is 1 gram. Process step is with embodiment 1.
实施例3Example 3
工艺条件为：原料脂肪酸的用量为100克，酸价大于180(毫克KOH/克样)，不饱和脂肪酸含量为88.5％；硫酸化反应温度在20℃～30℃范围；硫酸化反应时间为90分钟；浓硫酸加入量为15克；选矿起泡剂加入量为0.4克。工艺步骤同实施例1。The process conditions are: the amount of raw fatty acid is 100 grams, the acid value is greater than 180 (mg KOH/gram sample), and the unsaturated fatty acid content is 88.5%; the sulfation reaction temperature is in the range of 20°C to 30°C; the sulfation reaction time is 90 Minutes; the added amount of concentrated sulfuric acid is 15 grams; the added amount of beneficiation foaming agent is 0.4 grams. Process step is with embodiment 1.
实施例4Example 4
工艺条件为：原料脂肪酸的用量为100克，浓硫酸加入量为8克，选矿起泡剂2号油加入量为0.5克，其他工艺条件同实施例2。工艺步骤同实施例1。Process condition is: the consumption of raw material fatty acid is 100 grams, and the concentrated sulfuric acid add-on is 8 grams, and No. 2 oil add-on of beneficiation foaming agent is 0.5 gram, and other process conditions are with embodiment 2. Process step is with embodiment 1.
实施例5Example 5
工艺条件为：原料脂肪酸用量为100克，浓硫酸加入量为5克；选矿起泡剂2号油加入量为0.8克，其他工艺条件同实施例2。工艺步骤同实施例1。The technological conditions are: the raw material fatty acid consumption is 100 grams, the concentrated sulfuric acid addition is 5 grams; the no. Process step is with embodiment 1.
实施例6Example 6
加入的选矿起泡剂为三乙氧基丁烷，其他工艺条件同实施例2。工艺步骤同实施例1。The ore dressing foaming agent added is triethoxybutane, and other processing conditions are the same as in Example 2. Process step is with embodiment 1.
实施例7Example 7
加入的选矿起泡剂为聚丙烯三醇醚，其他工艺条件同实施例2。工艺步骤同实施例1。The beneficiation foaming agent added is polypropylene triol ether, and other process conditions are the same as in Example 2. Process step is with embodiment 1.
本发明萤石浮选剂的制备方法所采用的设备为本技术领域人员熟知的常规设备。The equipment used in the preparation method of the fluorite flotation agent of the present invention is conventional equipment well known to those skilled in the art.
采用本方法制备成的萤石浮选剂，其凝固点在14℃～20℃范围，酸价在170～200(毫克KOH/克样)之间。产品中大部分保留了原料脂肪酸的性质，根据加酸量不同，有1/3～1/4与加入的浓硫酸发生了硫酸化反应生成硫酸化产物：
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|---|---|---|---|---|
| EP1944088A1 (en) * | 2007-01-12 | 2008-07-16 | Omya Development Ag | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazollum methosulfate |
| CN101507948B (en) * | 2009-04-03 | 2012-04-25 | 陕西新星浮选剂有限责任公司 | Collecting agent for floatation of fluorite under low-temperature condition |
| CN101712014B (en) * | 2009-12-08 | 2012-03-21 | 湖南省铸万有实业有限公司 | Multicategory-impurity single fluorite ore dressing method |
| CN102240601B (en) * | 2010-05-12 | 2013-11-13 | 北京君致清科技有限公司 | Method for using collector prepared from illegal cooking oil in fluorite flotation |
| CN101983776A (en) * | 2010-11-10 | 2011-03-09 | 湖北富邦化工科技有限公司 | Collophane low-temperature reverse flotation collector and preparation method thereof |
| CN102755933A (en) * | 2011-04-29 | 2012-10-31 | 沈阳铝镁设计研究院有限公司 | Preparation method of collecting agent suitable for bauxite direct flotation |
| CN102764700B (en) * | 2012-08-01 | 2013-09-25 | 中钢集团马鞍山矿山研究院有限公司 | Preparation method of low temperature resisting fluorite flotation collector |
| CN102861665A (en) * | 2012-09-20 | 2013-01-09 | 浙江武义神龙浮选有限公司 | Method for producing fluorite concentrate by regrinding and re-cleaning fluorite tailings |
| CN103341412A (en) * | 2013-07-01 | 2013-10-09 | 湖南鑫源矿业有限公司 | Fluorite mine flotation collecting agent |
| CN104056726B (en) * | 2014-06-12 | 2016-12-07 | 北京矿冶研究总院 | Fluorite collecting agent and preparation method thereof |
| CN104475263B (en) * | 2014-11-24 | 2017-07-14 | 西北矿冶研究院 | Fluorite ore flotation collecting agent |
| CN109433426A (en) * | 2018-12-25 | 2019-03-08 | 郑州智锦电子科技有限公司 | Oxide ores mineral collectors such as a kind of collecting fluorite and preparation method thereof |
| CN113441285B (en) * | 2021-08-11 | 2022-09-23 | 浙江工业大学 | A kind of fluorite flotation collector and preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1369805A1 (en) * | 1985-11-13 | 1988-01-30 | Предприятие П/Я А-1997 | Method of flotation of fluorite-containing nonsulphide ores |
| SU1577845A1 (en) * | 1987-04-13 | 1990-07-15 | Сибирский государственный проектный и научно-исследовательский институт цветной металлургии | Method of flotation of fluorite-bearing ores |
-
1996
- 1996-04-30 CN CN96116909A patent/CN1052923C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1369805A1 (en) * | 1985-11-13 | 1988-01-30 | Предприятие П/Я А-1997 | Method of flotation of fluorite-containing nonsulphide ores |
| SU1577845A1 (en) * | 1987-04-13 | 1990-07-15 | Сибирский государственный проектный и научно-исследовательский институт цветной металлургии | Method of flotation of fluorite-bearing ores |
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| Publication number | Publication date |
|---|---|
| CN1150065A (en) | 1997-05-21 |
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